应用化学2017，Vol.34Issue(5)：572-581,10.DOI:10.11944/j.issn.1000-0518.2017.05.160353
异构的蒽乙烯单钌配合物:合成与表征、电化学、光谱性质及理论计算
Synthesis, Electrochemical and Spectral Properties, Theoretical Calculations of Isomeric Anthracene Vinyl Mononuclear Ruthenium Complexes
摘要
Abstract
Anthracene vinyl mononuclear ruthenium isomeric complexes 1 and 2 were synthesized from 9-ethynylanthracene and 2-ethynylanthracene, carbonylchlorohydridotris(triphenylphosphine) ruthenium(Ⅱ)[RuHCl(CO)(PPh3)3] and trimethylphosphine(PMe3) for ligand exchange, The structure of complex 2 was further confirmed by X-ray single crystal diffraction.Their electrical and optical properties were investigated in combination with theoretical calculations.Electronic structures of complexes 1 and 2 from density functional theory(DFT) optimization show that ruthenium vinyl and anthracene ring have different configurations in two isomers.Frontier molecular orbitals from DFT calculations feature that electron delocalized over the whole molecule in HOMO, and with larger proportion(90%) in anthracene vinyl parts.This suggests that anthracene vinyl ligand mainly participate in redox process.Electrochemical studies indicate that redox reversibility of complex 1 is lower than that of complex 2.Electronic absorption spectra of complexes 1, 2 and precursor molecules 1b, 2b exhibit obvious changes.The absorptions in UV region of complexes 1 and 2 collapse in comparison with that of molecules 1b and 2b, and appear a weak and broad absorptions in long wavelength direction, which are assigned to π→π* and metal-to-ligand charge-transfer(MLCT) absorptions from highest occupied molecular orbital(HOMO)→lower unoccupied molecular orbital(LUMO) transitions by time-dependent DFT(TDDFT) calculation.The fluorescence emission spectrum reveals that fluorescence intensity and fluorescence quantum yields drop sharply after the ruthenium coordinate to anthracene vinyl.CCDC of complex 2:1488284.关键词
蒽乙烯基/单钌配合物/电化学/光谱性质/密度泛函理论及含时密度泛函理论计算Key words
anthracene vinyl/monoruthenium complex/electrochemistry/spectrum properties/density functional theory and time-dependent density functional theory calculations分类
化学化工引用本文复制引用
欧亚平,张静,朱小明..异构的蒽乙烯单钌配合物:合成与表征、电化学、光谱性质及理论计算[J].应用化学,2017,34(5):572-581,10.基金项目
功能金属有机材料湖南省普通高校重点实验室开放基金资助(GN15K05),衡阳师范学院科学基金资助(14B23) （GN15K05）
Supported by Opening Subjects of Hunan Province Key Laboratory of Functional Organometallic Materials(No.GN15K05), the Scientific Research Foundation of the Hengyang Normal University(No.14B23) （No.GN15K05）
